Bleached and dyed furs and the like



e-ni sa 'Fieesas xa h64578 Ufl l muuuu m ca-qua; IULIIO Dec. K A 195 tress Reference UNITED STATES PATENT OFFICE.

HY MAN STEIN, ARVERNE. WILLIAM E. AUSTIN, OF NEW YORK, AND IRVING LTIEBOWITZ, OF BROOKLYN, NEW YORK, ASSIGNORS TO STEIN FUR DYEING CO. 1120., OF NEW YORK, N. Y., A CORPORATION OF NEW YORK.

. i No Drawing. Application filed May 3,

TIM [Z whom it IIN/j/ concern:

Be it known that we. HYM'AN STEIN, VIL- LL-ut E. AUSTIX. and Invrxo LII-IBOWITZ, citi- Zens of the United States, residing, respectively, in Arverne, Queens County, city and State of New York, in the borough of the Bronx. Bronx County, city and State of New York, and in the borough of Brooklyn. Kings County, city and State of New York. have invented an Improvement i n Bleached and Dyed Furs and the like, of which the following is a specification.

Our present invention relates to fibrous materials. particularly of animal origin, such as fur skins and the like. and more particularly such products in a condition which renders them remarkably well suited and adapted to be bleached with little or no impairment of their strength, texture and lustre. our invention relating also to the bleached and dved products themselves. It is an object of the presentinvention to provide articles of the general character designated above which shall be in a condition admirably adapting them for their subsequent conversion into bleached and 'dyed products, and alsoto provide the'bleached products in a remarkably fine condition as to lightness of color. but without loss of strength or impairment of their lustre and texture, the strength, lustre and texture of the bleached and dyed skins of the present invention being even improved. in certain cases, as compared with the skins dyed by the usual proc esses.

In the accompanying specification we sllftll describe an illustrative embodimentof the article of the presentinvention. It is, lltHYQTQI', to be clearly understood that our invention is not limited to the specific embodiment thereof herein described for purposes of illustration only. In the accompanying specificationwe shall also describe a method of producing the article of the present invention. which method. however,

is more fully destribed and is claimed in our eopending application filed by us of even date herewith and entitled Processes of BLEACHED AND DYED FURS AND THE LIKE.

1924. Serial No. 710,830.

bleaching and dyeing furs and the like, Serial No. 710,82 I

The articleozt. thepresent invention, in its unbleached condition. in which condition, however, it is admirably adapted and suited for the subsequent bleaching operation. which operation may be carried out on such article without destroying or even impairing its strengtlntexture and lustre, is characterized by incorporating in the voids or interstices of the fibres of the fur skin or like article a protective agent. By a protective agent we mean, in the present instance. anagent which, while permitting the desired bleaching or decolorizing operation to be carried out efiiciently and even with remarkable rapidity, protects the fibres of the fur skin or equivalent article from any destructive or weakening action of the bleaching agent. Such protective agents are preferably of mineral origin and preferably comprise reducing agents, such as ferrous compounds. An example of a protective agent which we have found particularly useful is ferrous sulphate.

The product, in ifigilll lleached..c.ondition, may be ohtained by soaking the fur skin or the like, preferably after it has previously been washed or killed by treatment for from about two to about three hours in an alt-almolntigm h such as a solution of sodium c'arbonate iu solution of the protectiviigfita"i n anaqueous solution containing from about 0. 5 to about 5.0% crystallized ferrous sulphate, weight. Since-the protective agentis generally a reducing agent which would tend to become oxidized by exposure to the air, we prefer to add to the solution of the protective agent a stabilizing agent, which, in the case where the protective agent comprises a ferrous salt, such as ferrous sulphate, preferably consists of ammonium chloride added in an amount approximately equal to the ferrous sulphate used and equal to from about 0.5 to about 5.0 per cent. by weight. The fur skin or the like is soaked in thesolution of the protective agent,=witb or without the added stabi- Search Room hydro-extracted.

lizing agent, overnight, or from about eight to about twelve hours.

By this treatment the voids or interstices of the skin become filled with the solution of the protective agent, which may or may not contain the stabilizing agent. .After this treatment the skins are rinsed and It will therefore be noted that the skins treated with the solution of the protective agent contain such agent in the inner voids or interstices of-the fibres of the skin or the like, rather than merely on the surfaces of such fibres. This is of great importance since it is one of the factors, in our opinion, although we do not wish to be limited to any particular theory or explanation of why the results of the present invention are obtained, which enables the subsequent bleaching operation to be carried out with little or no impairment of the strength of the fibres and of their fine lustre and texture.

y The unbleached product described above iis characterized by its remarkable adaptability to the subsequent bleaching operation, which operation may be carried out by the use of any suitable bleaching agent, but preferably by the use of hydrogen per oxide, or of sodium peroxide or sodium perborate, which latter are capable of yielding hydrogen peroxide in solution in the presencfofdiber ating agents, generally of an acid character. Not only may the bleaching operation be conducted without impairment of the strength of the fibres or of their texture or lustre, but instead of requiring ,from about 24 to 72 hours, as had been the Cease previously for obtaining even the imperfect and unsatisfactory products of the W bleaching processes as hitherto practiced,

(the unbleached product of the present invention described above requires only a fraction of this time for its proper and completely. satisfactory bleaching.

The bleached product is characterized by the remarkable strength of the leather, and the remarkable strength, fine texture and lustre of the hair of the fur skin or the like.

the same time the pigment or color originally present in the fur skin will have been removed, in whole orin part, without, however, destroying or .even impairing the strength, texture and lustre of the skin.

The bleached product described above may now be dyed to any light or other suitable color, hitherto obtainable only by dyeing natural white or light colored skins, by dyeing such skins in accordance with the usual dyeing processes customarily employed either for natural white or light colored skins,"-and with or without the use of a mordant. The dyed skins are characterized by their great strength and remarkably fine texture and lustre. The strength, texture and lustre, as Well as the general appearance, of the dyed skins of the presentinvention are such as to render it difficult for all but experts, and often even for experts, to distinguish the dyed skins of the present invention from the dyed natural white or light colored skins as hitherto manufactured and sold. The dyed product of the present in vention can therefore be sold at a price comparing favorably with the price of the dyed natural white or light colored skins, while costing much less, since it is manufactured flrom the comparatively cheap dark colored sun.

' While the process for making the product of the present invention is more fully described and claimed in our copending appli cation referred to above, it may be desirable, for the sake of a complete and full disclosure in the present case, to briefly summarize one specific illustrative example of the process, it being understood that the process is of general application and is not limited to the specific embodiment thereof herein described for purposes of example merely:

Brown moufilons are washed or killed in an alkaline solution, for example, a solution of sodium carbonate. This washing operation ordinarily requires from about 2 to about 3 hours. The washed or killed skins are then rinsed and thoroughly hydroextracted. The skins are then immersed in a solution of the protective agent, such as in a solution of ferrous sulphate, and there allowed to;; remain over night. While the strength of the ferrous sulphate solution or its equivalent may vary within considerable limits, we prefer to use an aqueous solution of ferrous sulphate of a strength of from about 0.5 to 5.0 per cent of the solid crysta1- lized ferrous sulphate, by weight. Such a solution may or may not contain the stabilizing agent. If a stabilizing agent, such as ammonium chloride, is used, we prefer t use it in an amount approximately pro'por tionate to the amount of ferrous sulphate used and equalling from about 0.5 to about 5.0 per cent of ammonium chloride, by weight.

The fur skins or the like, after having been soaked for from about 8 to about 12 hours in the solution of the protective agent, with or without the addition of the stabiliz- 8. BLEABHENG a meme; t-tuiu mention a Catalan Moran.

cause at names & FIBERS, .378

1 ling agent, are then rinsed and hydro-extract ed. The treatment apparently impregnates or fills the voids and interstices of the fibres with the solution of protective agent. The fur skins thus treated are now immersed in a solution of hydrogen peroxide or equivalent bleaching agent. However, in place -of hydrogen peroxide. we may use other bleaching agents, particularly sodium peroxide or sodium perborate, which yield hydrogen peroxide in solution in the presence of certain liberating agents, generally of an acid character. The amount of hydrogen peroxide used may vary from about five (5.0) to about one hundred (100.0) per cent by volume of a three (3.0) per cent solution of hydrogen peroxide. \Ve prefer that the temperature at which the bleaching or decolorizing operation is carried out shall be between and 100 F.

The skins are subjected to the action of the bleaching or decolorizing agent until they have been sulliciently decolorized. The bleached or decolorizcd skins are then rinsed and can. if desired, be dyed directly in accordance with any of the well known or desirable processes employed for dyeing furs or the. like. 'e may, however, subject the bleached or decolorized skins to the usual dyeing operations of washing and mordanting, and then dyeing the washed and mordanted skins in accordance with the practice hitherto generally employed for dyeing furs.

The advantages and superiorities of the product of the present invention in its various stages unbleached. bleached, and tlycdare numerous and of great practical importance, and may be briefly summarized as follows: The unbleached product, which may be sold as such and sent to any bleachcry for bleaching furs in accordance with the prin iples of the present invention, is characterized by containing in its pores, voids or interstices, a protective. agent, with or without a stabilizing agent, and being thus admirably suited and adapted for the bleaching operation. By means of the presence of the protective agent, with or without the stabilizing agent, in the fibres of the fur skin or the like, the bleaching operation may be conducted simply, conveniently, economically and very expeditiously, requiring only a fraction of the time hitherto required for the imperfect and unsatisfactory bleaching processes as customarily practiced. It may here be stated that hile the protective agent, with or Without the stabilizing agent. protects the fibres from destructive action of the bleaching agent. it at the same time greatly accelerates the desired bleaching action.

i The bleached, but undyed, skin is characterized by its great strength and by its remarkably fine texture and lustre, and contains in its interstices the protective agent,

'in relatively small amounts.

lieterentie by this time raised from a lower to a higher state of oxidation by the action of the hydrogen peroxide or other oxidizing bleaching agent. The bleached skin will be found to be remarkably well adapted to be subjected to the subsequent dyeing operation, which dyeing operation may be conducted with or without the use of a mordant.

The dyed product is characterized b having the strength, texture, lustre and appearance of the dyed natural white or light colored skin. For this reason, the dyed skin finds a wide and ready market and a ready sale at a price much greater than the dyed dark colored skin would fetch in the market and at a price comparing very favorably with the price of the dyed natural white or light colored skins.

It may here be stated that in addition to the mineral protective agent, such as the ferrous sulphate, with or without the addition of the stabilizing agent, the solution for giving the fur skins or the like their protective treatment for the subsequent bleaching operation may contain other compatible metal salts, as well as suitable protective colloids, such as glue, gelatin, or the like, generally Itmay here also be stated that the method described above may be applied with almost equal success in the treatment of skins whiclrhave already been dyed, either a dark or a light color, and whether satisfactorily or not. but preferably skins which have been dyed by the use of'a mordant consisting of a ferrous compound, such as ferrous sulphate, or an equivalent substance, thus producing from the previously dyed skins the superior prod uctdescribed above.

Vhat we claim as out-invention is:

.1. As an article of manufacture, an unbleached fur skin or the like suitable for bleaching and being in'ipregnated with a solution'of a protecting agent to protect the skin against harmful oxidation during a subsequent bleaching operation.

2. As an article of manufacture. an unbleached futf skin or the like suitable for bleaching and being impregnated with a solution of a mi neral reducing agent.

3. As an article of manufacture, an unbleached fur skin or the like suitable for bleaching and being impregnated with a solution of a ferrous salt.

4. As an article of manufacture, an unbleached fur skin or the like suitable for bleaching and being impregnated with a solution ofa mineral reducing agent to which has been added a stabilizing .agent.

As an article of 'manut'acture, an unbleached 'fur skin or the like suitable for bleaching and being impregnated with a solution of a ferrous salt to which has been added astabilizing agent.

6. As an article of manufacture, an un- Search Home bleached fur skin or the like suitable for bleaching and being impregnated with a solution-of a protectin agent to which has been added an agent for stabilizing the protecting agent to protect the skin against harmful oxidation during a subsequent bleaching operation.

7. As an article of manufacture, an unbleached fur skin or the like adapted for bleaching and containing in its fibres a mineral reducing agent.

8. As an article of manufacture, an unbleached fur skin or the like adapted for bleaching and containing in its fibres a ferrous compound.

9. As an article of manufacture, an unbleached fur skin or the like adapted for bleaching and containing in its fibres a mineral reducing agent and a stabilizing agent.

10. As an article of manufacture, an un' bleached fur skin or the like adapted for bleaching and containing in its fibres a ferrous compound and ammonium chloride.

11. As an article of manufacture, a

bleached fur skin or the like the fibres of which contain a protecting agent converted from a lowerto a higher state of oxidation by the bleaching agent, said protecting agent having served to protect the skin from harmful oxidation under the action of said 1 bleaching agent.

12. As an article of manufacture, a bleached fur-skin or the like the fibres of which contain a mineral protecting agent converted from a lower to a higher state of oxidation by the bleaching agent, said protecting agent having served to protect the skin from harmful oxidation under the action of said bleaching agent.

13. As an article of manufacture, a

bleached fur skin or the like the fibres ofwhich contain a mineral protecting agent in the form of an iron compound converted from the ferrous to the ferric state of oxidation by the bleaching agent, said rotecting agent having served to protect t 1e skin from harmful oxidation under the action of said bleaching agent.

14. As an article of manufacture, a bleached fur skin or the like the fibres of which contain a mineral protecting agent converted from a lower to a higher state of oxidation by hydrogen peroxide, said protecting agent having served to protect said skin from excessive oxidation under the action of the hydrogen peroxide.

15. As an article of manufacture, a bleached fur skin or the like the fibres of which contain a mineral protecting agent in mineral 16. As an article of manufacture, a

bleached fur skin or the like the fibres ofv which contain at protecting agent converted from a lower to a higher state of oxidation by hydrogen peroxide, said protecting agent having served to protect'sald skin from excessive oxidation under the action of the hydrogen peroxide.

17. As an article of manufacture, a

bleached and dyed fur skin or the like havandcontaining an iron compound raised from a lower to a higher state of oxidation by the bleaching agent before the fur skin. or the like has been dyed.

19. As an article of manufacture, a bleached and dyed fur skin or the like having the fibres of the leather and hair makingup the fur skin or the like substantially unimpaired as to strength, texture and lustre and containing an iron compound raised from a lower to a higher state of oxidation by the hydrogen eroxide or otherbleaching zligelt before the ur skin or the like has been 20. As an article of manufacture, a bleached and d ed fur skin or the like having the fibres o the leather and hair making up the fur skin or the like substantially unimpaired as to strength, texture and lustre. and having the appearance, feel and texture of a fur skin or the like of the same species dyed to the same color from the natural white or other light colored fur skin or the like.

21. As an article of manufacture, an unbleached fur skin or the like suitable for bleaching and being impregnated with a 1protecting agent to protect the skin against armful chemical action during a subsequent bleaching operation.

22. As an article of manufacture, an unbleached fur skin or the like suitable for bleaching and being impregnated with a mineral protecting agent to which has been added an agent for stabilizing the protecting agent to protect the skin against harmful chemical action during a subsequent bleaching operation. V

23. As an article of manufacture, a bleached and dyed fur skin or the like containing the dye stuff in combination with a metallic protecting compound raised from a lower to a. higher state of oxidation by the hydrogen peroxide or other bleaching agent before the fur skin or the like has been dyed, said protecting compound having served to protect the skin against harmful chemical action during the bleaching operation.

24. As an article of manufacture, a bleached and dyed fur skin or the like containing the dye stuff in combination with a metallic protecting compound raised from a lower to a higher state of oxidation by the bleaching agent before the fur skin or the ke has been dyed, said protecting compound having served to protect the skin 0 4 DISCLAIMER ast ma-K m Stein, Arverne, William E. Austin, New York, and Irving Liebowitz, Brooklyn, N. Y. 'BLEACHED AND DYED FURs AND THE LIKE.

Dated December 8, 1925-. Patents Corporation.

Patent Disclaimer filed May 3, 1933, bythe assignee, Steinfm' Hereby entersthis disclaimer to that part of theclaims in said specification which is in thefollowing words, .to wit:

17. As an article of manufacture, ableached and dyed fur skin or the like having the fibres of the leather and hair making up the fur skin or the like substantially unimpaired as to strength, textureand lustre.

20. As an article of manufacture, a bleached and dyed fur skin or the likehaving the fibres of the leather and hair making up the fur skin or the like substantially unimpaired as to strength, texture and lustre, and having the appearance, feel and texture of a fur skin or the like of the same species 'dyed to the same color from the natural white or other light colored fur skin or the like.

[Oficial Gazette May 30, 1933.] 

